CN1860212A

CN1860212A - 3-isopropyl-1-methylcyclopentyl derivatives and their use in fragrance applications

Info

Publication number: CN1860212A
Application number: CNA2004800281885A
Authority: CN
Inventors: J·A·巴克洛维克兹
Original assignee: Givaudan SA
Current assignee: Givaudan SA
Priority date: 2003-09-30
Filing date: 2004-09-29
Publication date: 2006-11-08
Anticipated expiration: 2024-09-29
Also published as: CN100552010C; DE602004009814D1; ATE377066T1; BRPI0414884A; EP1668102B1; DE602004009814T2; US20070054836A1; JP2007507434A; ES2295900T3; EP1668102A1; GB0322750D0; WO2005030914A1; MXPA06003263A

Abstract

This invention relates to -3-isopropyl-1-methylcyclopentyl derivatives of formula (Ia) and (Ib), where R<1>, R<2> and R<3> are as defined in the claims, and their use in fragrance applications.

Description

3-sec.-propyl-1-methylcyclopentyl derivative and the purposes in fragrance application thereof

The present invention relates to 3-sec.-propyl-1-methylcyclopentyl derivative, i.e. (3-sec.-propyl-1-methylcyclopentyl) ethanol, (3-sec.-propyl-1-methylcyclopentyl) ethyl ketone and (3-sec.-propyl-1-methylcyclopentyl) methyl alcohol, and they are as the purposes of perfume compound.The invention still further relates to their production method and contain their fragrance composition.

In the perfume compound field, always demand can strengthen or improve the smell sense of taste or can give the compound of new fragrance.

Find at present, some 3-sec.-propyl-1-methylcyclopentyl derivative has the very popular fragrance of a flower, fruit perfume (or spice) and banksia rose fragrance, and they prepare relatively simple and easily, and starting raw material of its preparation usefulness is naturally occurring (1S)-(+)-and (1R)-(-)-fenchone.

Therefore, one aspect of the present invention relate to the compound of following formula 1a and its enantiomer promptly (1R, 3S)-enantiomer is as the purposes of perfume compound:

R wherein ¹Be hydrogen or methyl;

R ²Be hydrogen; And

R ³It is hydroxyl; Perhaps

R ²And R ³Form carbonyl with the carbon atom that links to each other with them.

It is found that the average twice of the threshold odour number of some compound of formula 1a is lower than corresponding enantiomer.Therefore, be rich in formula 1a (1R, 3S) compound of the following formula I of enantiomer is preferred.

Use term " to be rich in " herein to be meant for selected enantiomer enantiomeric purity greater than 1: 1 compound.Had about 1: 3 or bigger purity, for example about 1: 4 compound is preferred.Particularly preferably be and had 1: 9 or the compound of bigger enantiomeric purity, as 5: 95 or 1: 99.

Particularly preferred compound of the present invention be [(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol, 1-[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethyl ketone and 1～[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethanol.

Compound of the present invention can use separately or unite use with basic material.Herein, " basic material " comprises all known fragrance molecules, be selected from present obtainable natural product widely and synthetic molecules, essential oil class for example, alcohols, aldehydes and ketone, ethers and acetals, ester class and lactone, ring and heterocyclic greatly, and/or the composition that in fragrance composition, is used in combination with one or more routines or vehicle with sweetener for example the carrier substance blending use and other this area assistant agent commonly used.

Below listed material comprise the example of the known fragrance molecule that can be used in combination with The compounds of this invention:

-ether system oil and extract, tree moss absolute for example, basil oil, castoreum oil, costus root oil, myrtol, oak moss absolute, Herba Erodii oil, jasmine absolute, patchouli oil, rose oil, santal oil, wormwood oil, oleum lavendulae or ylang-ylang oil;

-alcohols, geraniol for example, Ebanol ^TM, oxymethoxyallylbenzene, farnesol, Geraniol, Super Muguet ^TM, phantol, phenylethyl alcohol, Sandalore ^TM, terpinol or Timberol ^TM

-aldehydes and ketone, α-Wu Jirouguiquan for example, Georgywood ^TM, laurine, Iso E Super , Isoraldeine , Hedione , voitol, methyl cypress base ketone, methyl ionone or Vanillin;

-ether and acetals, for example Ambrox ^TM, geranyl methyl ether, rose oxide or Spirambrene ^TM

-ester class and lactone, jasmal for example, cedryl acetate, γ-decalactone, Helvetolide , γ-Shi Yineizhi or vetiveryl acetate.

-macrocycles, cyclohexa decen-7-olide for example, ethylene brassylate or Exaltolide .

-heterocycles, for example Isobutylquinoline.

Compound of the present invention can use in the fragrance application widely, for example in any field of fine perfumery and functional spices, and for example perfume, household product, laundry product, body care products and cosmetics.Compound can be to use with the amount of wide variations scope, and this depends on the character and the quantity of concrete application and other flavouring composition.Usage ratio generally be articles for use about 0.001 to about 20wt%.In one embodiment, compound of the present invention can the amount with about 0.001-0.05wt% use in fabric softener.In another embodiment, compound of the present invention can be with about 0.1-20wt%, the more preferably from about amount use of 0.1-5wt% in fine perfumery.Yet these numerical value only are that the mode with example provides, and maybe may produce new humorous perfume (or spice) because exper ienced spices allotment person uses lower or higher concentration also can be effective.

Compound of the present invention can be used for fragrance application, simply by fragrance composition is directly mixed with fragrance application, perhaps, they can be held back with trapped material in step formerly, described trapped material is polymkeric substance, capsule, microcapsule and nanocapsule, liposome, membrane-forming agent, absorption agent such as carbon or zeolite, cyclic oligosaccharide and composition thereof for example, perhaps can be with them and substrate chemical bonding, make when applying outside stimulus, during as light, enzyme etc., substrate can discharge aromatic molecules, mixes with articles for use then.

Therefore, the present invention additionally provides a kind of method for preparing fragrance application, comprise that admixture is rich in the formula I compound of one of its enantiomer as fragrance ingredient, described admixture passes through the direct blending of compound to articles for use, the fragrance composition that perhaps contains the formula I compound that is rich in one of its enantiomer by blending uses conventional technology and method that it is mixed in the fragrance application then.

Herein, " fragrance application " is meant any product, as fine perfumery, and for example perfume and astringent (Eau de Toilette); Household product, for example washing composition of use in dishwasher, surface cleaner; Laundry product, for example softening agent, SYNTHETIC OPTICAL WHITNER, stain remover; Body care products, for example shampoo, bath gel; And cosmetics, for example reodorant, vanishing cream comprise sweetener.These listed products are to illustrate that mode provides and not limit the present invention in any way.

Compare the most of fragrance molecule with fragrance of a flower odour characteristics of this area, laurine, Geraniol, phantol and 4-(4-hydroxy-4-methyl amyl group) hexamethylene-3-alkene-1-formaldehyde for example, the present invention is R wherein ³The formula 1a compound that is hydroxyl all is especially stable under alkaline condition or under acidic conditions, therefore makes them be specially adapted to a lot of various types of fragrance application.

The preparation of formula 1a compound and enantiomer thereof can be for example by (1R)-(-)-fenchone/(1S)-(+)-fenchone (1,3,3-trimethylammonium-2-norbornane ketone) Haller-Bauer resets, then under alkaline condition, for example in the presence of the alkali of NaOH or KOH, be hydrolyzed into 3-sec.-propyl-1-methylcyclopentane carboxylic acid.Then, with gained acid and lithium methide reaction, obtain wherein R ²And R ³With the formula I compound that forms carbonyl with their continuous carbon atoms.For obtaining other compound of the present invention, can be by using for example NaBH ₄Reduction is transformed into secondary alcohol with the ketone of gained.

(3-sec.-propyl-1-methylcyclopentyl) methyl alcohol can prepare by 3-sec.-propyl-1-methylcyclopentane carboxylic acid (A) (its rearrangement by fenchone makes) is reduced into corresponding alcohol in the presence of LAH, shown in following response path:

Response path 1:

Optically pure formula 1a and 1b compound and the formula I compound that is rich in one of enantiomer are (promptly, the compound of formula 1a or 1b) enantiomeric mixture can be synthesized as starting raw material by optically pure fenchone or by the enantiomeric mixture that is rich in (1R)-(-)-fenchone or (1S)-(+)-fenchone.

Below with reference to following indefiniteness embodiment the present invention is described.

All the finished product are water white oil described in following examples 1-6.They are by (1R)-(-)-and (1S)-(+)-fenchone is initial to be obtained, and wherein said (1R)-(-)-and (1S)-(+)-fenchone contains 8% and 2% another kind of enantiomer respectively.The NMR data of being reported are measured under following common conditions: ¹H in 400 times and ¹³C is under 100MHz; At CDCl ₃In; Chemical shift (δ) is in the downfield ppm of TMS; Coupling constant J is in Hz.

Embodiment 1:[(1R, 3S)-3 one sec.-propyls-1-methylcyclopentyl] methyl alcohol

Will (1R, 3S)-(it obtains (V.Braun, J. by (1R)-(-)-fenchone to 3-sec.-propyl-1-methylcyclopentane carboxylic acid for 70.0g, 0.41mol; Jacob, A.Chem.Ber.1933,66,1461)) solution in diethyl ether (100ml), (13.3g is 0.35mol) in the suspension in same solvent (500ml) slowly to be added into lithium aluminum hydride under condition of nitrogen gas.After the reflux 3h, reaction mixture is cooled to 10 ℃, carefully adds 2N NaOH solution (70ml) and continue to stir 0.5h.Filter white solid, with filtrate with the salt water washing (2 * 500ml), dry (MgSO ₄) and vacuum concentration.Use 10cm Vigreux post (0.9-1.1 millibar, 96-98 ℃), with crude product (79.0g) distillation purifying, obtain [(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol (57.0g, 90% productive rate).

¹H-NMR：δ0.87(d，J＝6.7，3H)，0.88(d，J＝6.7，3H)，1.01(s，3H)，1.08(dd，J＝12.3，11.0，1H)，1.16-1.38(m，3H)，1.48(ddd，J＝12.4，6.9，0.8，1H)，1.53-1.72(m，3H)，1.74-1.87(m，1H)，3.35(d，J _AB＝10.4，1H)，3.39(d，J _AB＝10.4，1H). ¹³C-NMR：δ21.5(2q)，25.0(q)，30.4(t)，33.8(d)，35.6(t)，41.5(t)43.8(s)，46.9(d)，72.1(t).[α] _D ²²-12.0(c1.0，EtOH).

Smell is described: the fragrance of a flower, and blue or green fragrant, jasmine perfume (or spice), lily of the valley perfume (or spice), novel aroma is fresh.

Embodiment 2:[(1S, 3R)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol

According to the experimentation of embodiment 1, prepare as starting raw material by (1S)-(+)-fenchone.

[α] _D ²²+13.5(c1.0，EtOH)。

Smell is described: the fragrance of a flower, and fruit perfume (or spice), blue or green fragrant, Muscat Hamburg, orange peel perfume (or spice) (grapefruit perfume (or spice)).

Embodiment 3:1-[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethyl ketone

Under 0 ℃, with 25 minutes time, with lithium methide in diethyl ether (200ml, 0.32mol) the 1.6M drips of solution in add to (1R, 3S)-(25.5g is 0.15mol) in the solution in THF (250ml) for 3-sec.-propyl-1-methylcyclopentane carboxylic acid.After 0 ℃ was down stirred 3h, add the chlorine trimethyl silane (151ml 1.2mol) and allow reaction mixture to be warmed to room temperature, was poured over (200ml) in the ice-cooled water, stirs 0.5h and extracts (2 * 250ml) with MTBE while cool off.With organic phase water (200ml), 2M NaOH (150ml) and salt solution (3 * 200ml) washings, the dry (MgSO that merges ₄) and vacuum concentration, obtain crude product 1-[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethyl ketone (27.6g), distill come purifying (0.93g, 68% productive rate) by ball to ball with its sample (1.5g).

¹H-NMR：δ0.89(2d，J＝6.6，6H)，1.19(s，3H)，1.24(dq，J＝12.4，9.1，1H)，1.34-1.43(m，2H)，1.56-1.77(m，3H)，1.81-1.90(m，1H)，2.09(ddd，J＝13.1，9.1，4.0，1H)，2.15(s，3H). ¹³C-NMR：δ21.3(q)，21.4(q)，25.0(q)，25.3(q)，30.2(t)，33.3(d)，35.6(t)，41.0(t)，46.6(d)，55.3(s)，213.0(s).[α] _D ²²-1.0(c?1.1，EtOH).

Smell is described: native perfume (or spice)/tongue perfume (or spice), and blue or green fragrant, the banksia rose.

Embodiment 4:1-[(1S, 3R)-3-sec.-propyl-1-methylcyclopentyl] ethyl ketone

According to the experimentation of embodiment 3, prepare as starting raw material by (1S)-(+)-fenchone.

[α] _D ²²+1.0(c?1.1，EtOH)。

Smell is described: the fragrance of a flower, and the native soil flavor, fruit perfume (or spice) is blue or green fragrant.

Embodiment 5:1-[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethanol

With the 1-[(1R of embodiment 3,3S)-3-sec.-propyl-1-methylcyclopentyl] (3.0g, 18mmol) solution in ethanol (8ml) is added into sodium borohydride (0.42g is 10.7mmol) in cold (ice bath) solution in same solvent (17ml) ethyl ketone.At room temperature stir after the 1.5h, reaction mixture is poured over ice-cooled 2M HCl (100ml) upward and with MTBE extracts (2 * 100ml).With the organic phase that merges with the salt water washing (2 * 50ml), dry (MgSO ₄) and vacuum concentration.Crude product (2.8g) is distilled purifying by ball to ball, and (diastereomer is than～1: 1) for 2.34g, 77% productive rate.

¹H-NMR：δ0.87(d，J＝6.6，3H)，0.875(d，J＝6.6，3H)，0.88(2d，J＝6.6，6H)，0.92(s，3H)，0.93(s，3H)，1.05(t，J＝11.7，1H)，1.12(d，J＝6.4，3H)，1.125(d，J＝6.4，3H)，1.14(t，J＝11.8，1H)，1.17-1.74(m，12H)，1.47(2s，2H)，1.78-1.88(m，2H)，3.53(q，J＝6.3，1H)，3.55(q，J＝6.3，1H). ¹³C-NMR：δ18.5(2q)，21.3(2q)，21.4(3q)，21.5(q)，29.8(t)，30.0(t)，33.7(2d)，35.8(t)，35.9(t)，41.9(2t)，46.3(2d)，46.8(s)，46.9(s)，75.4(d)，75.7(d).[α] _D ²²-7.0(c?1.0，EtOH).

Smell is described: the fragrance of a flower, and native perfume (or spice)/tongue perfume (or spice), slight Terpineol 350 flavor/soil is fragrant.

Embodiment 6:1-[(1S, 3R)-3-sec.-propyl-1-methylcyclopentyl] ethanol

According to the experimentation of embodiment 5, prepare as starting raw material by (1S)-(+)-fenchone.

[α] _D ²²+8.0(c?1.0，EtOH)。

Smell is described: orange peel perfume (or spice)/oranges and tangerines perfume (or spice), and fruit perfume (or spice), blue or green fragrant, novel aroma (grapefruit perfume (or spice), rheum officinale perfume (or spice)).

Embodiment 7: women's highclass perfumes

Composition * weight part

Geraniol 50

Xian Kelaiquan 15

Diethyl malonate 5

Dipropylene glycol (DPG) 149

Cyanine aldehyde (Florhydral) 12

Gardenol 10

Geraniol 50

Methyl dihydrojasmonate (Hedione) 25

Jasmonal H 200

Laurine 35

Isocyclocitral (1% in DPG) 15

Isojasmone 2

Jasmal 40

Jasmonyl 20

Lemon oil 10

LYRAL 25

Phantol 65

Phanteine 50

Methyldiantilis 2

Paraguay's Oils, bergamot peel 5

Phenylethyl alcohol 65

Silvial 100

[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol 50

Amount to 1000

* chemical name is referring to Flavor and Fragrance Materials-2003, AlluredPublishing Corp.Carol Stream III., U.S.A..

Exist 5% [(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol brings creamy, the fragrant feature of the lily of the valley to this prescription.

Embodiment 8: soap can thing with fragrance of a flower group

Composition * weight part

Agrumex 100

Benzophenone 60

Jasmal 55

Citrus bergamia base-material 80

Acetate 4-tertiary butyl cyclohexyl 150

Phenylate 20

Dipropylene glycol (DPG) 78

Ebanol 20

Laurine 200

Jasmine base-material 80

Methyl phenylacetate 2

Nerol 20

Phenylpropyl alcohol 40

Rose base-material 100

Rhodinol 65

Sandela 30

Silvial 100

[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol 50

Amount to 1250

[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol makes the fragrant soft and plentiful of this lily of the valley perfume (or spice).

Claims

1, following formula 1a compound and enantiomer thereof are as the purposes of perfume compound:

R wherein ¹Be hydrogen or methyl;

R ²Be hydrogen; With

R ³It is hydroxyl; Perhaps

2, the compound of claim 1 is as the purposes of perfume compound, wherein said compound is selected from: [(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] methyl alcohol, [(1S, 3R)-and 3-sec.-propyl-1-methylcyclopentyl] methyl alcohol, 1-[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethyl ketone, 1-[(1S, 3R)-and 3-sec.-propyl-1-methylcyclopentyl] ethyl ketone, 1-[(1R, 3S)-3-sec.-propyl-1-methylcyclopentyl] ethanol and 1-[(1S, 3R)-and 3-sec.-propyl-1-methylcyclopentyl] ethanol.

3, the compound of following formula I is as the purposes of perfume compound:

Wherein said formula I compound is rich in the enantiomer with following formula 1a:

R wherein ¹, R ²And R ³Have the identical meanings given as claim 1.

The compound of following formula I is as the purposes of perfume compound:

Wherein said formula I compound is rich in the enantiomer with following formula 1b:

R wherein ¹, R ²And R ³Have the identical meanings given as claim 1.

The purposes of the defined compound of one of aforementioned claim in fragrance application.

The fragrance application that contains aforementioned each defined compound of claim 1-4.

The fragrance application of claim 6, wherein fragrance application is perfume, household product, laundry product, body care products or cosmetics.

A kind of production method of fragrance application comprises the step of mixing defined formula Ia compound in the claim 1,2,3 and 4 or its enantiomer.

The compound of following formula 1a:

Wherein

R ¹Be hydrogen and methyl;

R ²Be hydrogen; With

R ³It is hydroxyl; Perhaps

The compound of following formula 1b:

Wherein

R ¹Be hydrogen and methyl;

R ²Be hydrogen; With

R ³It is hydroxyl; Perhaps